CA2581419A1 - System for gas separation and method for producing such a system - Google Patents
System for gas separation and method for producing such a system Download PDFInfo
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- CA2581419A1 CA2581419A1 CA 2581419 CA2581419A CA2581419A1 CA 2581419 A1 CA2581419 A1 CA 2581419A1 CA 2581419 CA2581419 CA 2581419 CA 2581419 A CA2581419 A CA 2581419A CA 2581419 A1 CA2581419 A1 CA 2581419A1
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- 238000000926 separation method Methods 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 6
- 239000010410 layer Substances 0.000 claims abstract description 70
- 239000011148 porous material Substances 0.000 claims abstract description 41
- 239000002346 layers by function Substances 0.000 claims abstract description 36
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 15
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims description 33
- 238000000034 method Methods 0.000 claims description 21
- 230000007423 decrease Effects 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims 2
- 229910052593 corundum Inorganic materials 0.000 claims 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims 2
- 239000012528 membrane Substances 0.000 description 47
- 239000007789 gas Substances 0.000 description 42
- 239000000919 ceramic Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 230000001419 dependent effect Effects 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229920005597 polymer membrane Polymers 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 101150071434 BAR1 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021124 PdAg Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 229940110728 nitrogen / oxygen Drugs 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- HKJYVRJHDIPMQB-UHFFFAOYSA-N propan-1-olate;titanium(4+) Chemical compound CCCO[Ti](OCCC)(OCCC)OCCC HKJYVRJHDIPMQB-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/024—Oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/22—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion
- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0048—Inorganic membrane manufacture by sol-gel transition
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0072—Inorganic membrane manufacture by deposition from the gaseous phase, e.g. sputtering, CVD, PVD
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/106—Membranes in the pores of a support, e.g. polymerized in the pores or voids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/108—Inorganic support material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/022—Asymmetric membranes
- B01D2325/0232—Dense layer on both outer sides of the membrane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
- Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
- Y10T428/2495—Thickness [relative or absolute]
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249961—With gradual property change within a component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
- Y10T428/249979—Specified thickness of void-containing component [absolute or relative] or numerical cell dimension
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/249921—Web or sheet containing structurally defined element or component
- Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
- Y10T428/249978—Voids specified as micro
- Y10T428/24998—Composite has more than two layers
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Dispersion Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Chemically Coating (AREA)
Abstract
The invention relates to a method for producing a device for gas separation, said device comprising a layer system wherein a functional layer consisting of Ti02 and/or Zr02 having an average pore diameter of less than 1 nm is applied to at least one side of a carrier layer that is porous throughout. Said carrier layer is preferably between 100 m and 1 mm thick and comprises continuous pores with an average pore diameter in the m range. The functional layer which is applied directly or by means of at least one intermediate layer comprises continuous pores with an average pore diameter of less than 1 nm, especially less than 0.8 nm. The functional layer can advantageously be embodied as a graduated layer. The invention is especially characterised by the symmetrical structure of the device, in which functional layers are applied to both sides of the carrier layer, optionally by means of respectively at least one intermediate layer.
Description
23856 PCT/DE2005/001442 Transl. of WO 2006/032230 SYSTEM FOR GAS SEPARATION AND METHOD
FOR PRODUCING SUCH A SYSTEM
The invention relates to a system for gas separation, in particular for separation of N2/O2r C02/H2, and N2/CO2 gas mixtures.
The invention further relates to a method for producing such a system.
Prior art Separation of media, in particular gases, is possible in principle by the use of membranes. A distinction is made between mesoporous membranes that have a pore diameter between 2 and 50 nm, and microporous membranes that have a pore diameter of less than 2 nm.
In mesoporous membranes, gas transport occurs via Knudsen diffusion, which is dependent on the adsorption properties of the membrane material. The separation factor for gas mixtures is generally low for such membranes.
For separation of individual gases from gas mixtures, the use of microporous membranes, such as silica membranes, is known from the literature. The gas separation is based on the principle of molecular sieves, in which a first gas from the gas mixture can pass through the membrane, but another gas cannot due to the greater kinetic molecular diameter. The driving force for the separation process is the pressure differential between the two gas spaces.
The most important parameters for gas separation membranes are their permeability and separation factors. These properties determine the separation efficiency and the membrane requirements for a separation task.
23856,PCT/DE2005/001442 Transl. of WO 2006/032230 At stationary conditions under the driving force for a partial pressure differential for a particle, a flow J (units: kg m- 2 s-1) results through a membrane portion having an area A. The permeability P of a membrane is expressed as the normalized volumetric flow per membrane area, time, and partial pressure differential for the permeating gas (units: nm3 (STP) m 2 h-1 bar-1, STP: 0 C, 101,325 Pa, 22.414 L molar volume).
The separation efficiency of a membrane material is given by the separation factor a. The separation factor for a gas pair is defined as the ratio of the gas permeabilities P, and is dependent on the temperature, feed pressure, and pressure differential over the membrane, as well as the pore diameter and pore distribution. As an approximation, separation factors are not dependent on the membrane thickness. Exceptions are membranes having very thin separation layers (< 0.1 m) compared to isotropic films (100 m) .
Gas permeation separates gas streams into streams of various components. Established industrial applications of gas permeation include the separation of hydrogen from process gas, nitrogen/oxygen separation from air, and recovery of organic vapors such as gasoline vapors from gas/air mixtures.
The use of gas permeation using inorganic membranes also shows promise. These include microporous membranes, such as multilayer silica membranes (amorphous Si02), zeolite membranes, or carbon membranes, as well as metallic membranes (PdAg alloy, for example) or perovskite membranes as mixture-conducting membranes.
The fields of application for inorganic membranes are numerous and 23856 PCT/DE2005/001442 Transl. of WO 2006/032230 diverse. They share the common feature of use under difficult process conditions such as high temperature and/or high pressure.
Typical applications of gas permeation using inorganic membranes are in particular the purification of gas streams necessary for subsequent process steps (risk of catalyst poisoning, for example), shifting of the reaction equilibrium by selective separation of products or by-products, and concentration of product streams for reducing the energy demand for subsequent end processing steps.
Membrane units frequently have a modular design, and may therefore be variably adapted to different objectives. In addition, different throughputs may be accommodated. Such membranes do not require movable parts, and as a rule are relatively light and compact.
High product purity can usually be obtained using the membrane process, but generally only with a comparatively great level of effort, since high selection rates, for example, are achieved only by dense membranes. Also from the operational standpoint, the membrane processes are restricted to relatively narrow pH, temperature, and moisture ranges due to, among other factors, the typically limited thermal and chemical stability of the membrane materials.
Ceramics having a selectively set porosity, for example, are known from the Fraunhofer Institute for Ceramic Technologies and Sintered Materials (IKTS) that are produced by sintering narrowly fractionated particles. Open, permeable pore volumes of 30-60 volume-% and narrow pore size distributions are obtained averaging in the micrometer or nanometer range.
FOR PRODUCING SUCH A SYSTEM
The invention relates to a system for gas separation, in particular for separation of N2/O2r C02/H2, and N2/CO2 gas mixtures.
The invention further relates to a method for producing such a system.
Prior art Separation of media, in particular gases, is possible in principle by the use of membranes. A distinction is made between mesoporous membranes that have a pore diameter between 2 and 50 nm, and microporous membranes that have a pore diameter of less than 2 nm.
In mesoporous membranes, gas transport occurs via Knudsen diffusion, which is dependent on the adsorption properties of the membrane material. The separation factor for gas mixtures is generally low for such membranes.
For separation of individual gases from gas mixtures, the use of microporous membranes, such as silica membranes, is known from the literature. The gas separation is based on the principle of molecular sieves, in which a first gas from the gas mixture can pass through the membrane, but another gas cannot due to the greater kinetic molecular diameter. The driving force for the separation process is the pressure differential between the two gas spaces.
The most important parameters for gas separation membranes are their permeability and separation factors. These properties determine the separation efficiency and the membrane requirements for a separation task.
23856,PCT/DE2005/001442 Transl. of WO 2006/032230 At stationary conditions under the driving force for a partial pressure differential for a particle, a flow J (units: kg m- 2 s-1) results through a membrane portion having an area A. The permeability P of a membrane is expressed as the normalized volumetric flow per membrane area, time, and partial pressure differential for the permeating gas (units: nm3 (STP) m 2 h-1 bar-1, STP: 0 C, 101,325 Pa, 22.414 L molar volume).
The separation efficiency of a membrane material is given by the separation factor a. The separation factor for a gas pair is defined as the ratio of the gas permeabilities P, and is dependent on the temperature, feed pressure, and pressure differential over the membrane, as well as the pore diameter and pore distribution. As an approximation, separation factors are not dependent on the membrane thickness. Exceptions are membranes having very thin separation layers (< 0.1 m) compared to isotropic films (100 m) .
Gas permeation separates gas streams into streams of various components. Established industrial applications of gas permeation include the separation of hydrogen from process gas, nitrogen/oxygen separation from air, and recovery of organic vapors such as gasoline vapors from gas/air mixtures.
The use of gas permeation using inorganic membranes also shows promise. These include microporous membranes, such as multilayer silica membranes (amorphous Si02), zeolite membranes, or carbon membranes, as well as metallic membranes (PdAg alloy, for example) or perovskite membranes as mixture-conducting membranes.
The fields of application for inorganic membranes are numerous and 23856 PCT/DE2005/001442 Transl. of WO 2006/032230 diverse. They share the common feature of use under difficult process conditions such as high temperature and/or high pressure.
Typical applications of gas permeation using inorganic membranes are in particular the purification of gas streams necessary for subsequent process steps (risk of catalyst poisoning, for example), shifting of the reaction equilibrium by selective separation of products or by-products, and concentration of product streams for reducing the energy demand for subsequent end processing steps.
Membrane units frequently have a modular design, and may therefore be variably adapted to different objectives. In addition, different throughputs may be accommodated. Such membranes do not require movable parts, and as a rule are relatively light and compact.
High product purity can usually be obtained using the membrane process, but generally only with a comparatively great level of effort, since high selection rates, for example, are achieved only by dense membranes. Also from the operational standpoint, the membrane processes are restricted to relatively narrow pH, temperature, and moisture ranges due to, among other factors, the typically limited thermal and chemical stability of the membrane materials.
Ceramics having a selectively set porosity, for example, are known from the Fraunhofer Institute for Ceramic Technologies and Sintered Materials (IKTS) that are produced by sintering narrowly fractionated particles. Open, permeable pore volumes of 30-60 volume-% and narrow pore size distributions are obtained averaging in the micrometer or nanometer range.
23856 PCT/DE2005/001442 Transl. of WO 2006/032230 Ceramic filtration membranes for liquid filtration and gas separation are produced by application, sometimes in multiple coatings, of thin layers having fine porosities onto a coarsely porous substrate. Such membranes are referred to as asymmetrical membranes. Typical substrates are tubes or multichannel elements.
The use of disks as substrates results in flat membranes.
The advantage of ceramic membranes compared to polymer filters is that use is made of the high thermal and chemical resistance of the ceramic.
Also known from the Fraunhofer Institute for Ceramic Technologies and Sintered Materials (IKTS) are polymer membranes having layer thicknesses that may be set between 1 and 5 m and that are produced by coating the substrate with a specially prepared organosilicon precursor, followed by polymer pyrolysis.
Various porosities and pore sizes are obtained, depending on the type and molecular structure of the polymer used. One precursor system results in, for example, pore diameters of approximately 1.5 nm with a narrow distribution, and BET surfaces of up to 600 m2/g. Pyrolysis of other polymer classes results in various pore diameters between 4 and 20 nm with a narrow pore size distribution, depending on the molecular structure and the thermolytic conditions. After pyrolysis an opaque, crack-free, highly porous silicon carbide layer is present on the substrate surface that is used as a filter-active separating layer in the membrane filtration process.
For gas phase separation of commercially important gases emitted from a fossil fuel-fired power plant, there are currently over 40 different approaches, of which only the chemical separation 23856 PCT/DE2005/001442 Transl. of WO 2006/032230 technology, i.e. absorption in amine solutions in pilot power plants, has thus far been used on an industrial scale.
For separation by set pore sizes, polymer membranes have been developed for separation in the low-temperature range.
Hydrogen-permeable AgPd membranes and amorphous microporous silica membranes, for example, exist for high-temperature applications up to approximately 500 C. Ionic, mixed, or proton conductors may also be considered.
It is disadvantageous that the chemical processes generally have a high loss in efficiency, whereas the polymer membranes are limited to applications at low temperatures. The maximum operational limits for costly AgPd membranes and for silica membranes is approximately 500 C. It is disadvantageous that these membranes are also sensitive to water.
Object and solution The object of the invention is to provide a system that allows gas separation of commercially important gases such as H2, N2, 02, or CO2 from a gas mixture, in particular at higher temperatures. It is a further object of the invention to provide a method for producing such a system.
The objects of the invention are attained by a system comprising the totality of features according to the main claim, and by a method comprising the totality of features of the independent claims. Advantageous embodiments of the method and the system are given in the subclaims that respectively refer to the main and/or independent claims.
Subject matter of the invention Within the scope of the invention it has been found that a thin membrane comprising a metallic and/or ceramic substrate 23856 PCT/DE2005/001442 Transl. of WO 2006/032230 layer and an oxidic functional layer provided thereon has an effective separation factor for the separation of gases.
The substrate layer has an advantageous effect on the mechanical stability of the membrane, and in particular may be composed of steel, for example 316 L stainless steel and/or a ceramic. The thickness of the substrate layer depends on the separation task, and may vary between 100 pm and 1 mm. The thickness of the substrate layer influences the permeation rate, and in principle should therefore be as thin as possible, in particular less than 1 mm. However, in order to meet their function as a substrate layer it is desirable and advantageous to have layer thicknesses of at least 100 m, preferably 200 pm.
Metallic substrate layers generally have better stability than ceramic layers of a comparable layer thickness.
The substrate layer itself has a porous structure throughout, with an average pore size in the m range. The average pore diameter may be determined in particular by scanning electron microscopy (SEM), or, for smaller pore diameters, by transmission electron microscopy (TEM). The pores are selected to be much larger than those in the adjacent functional layer. The substrate layer should provide mechanical stability while producing the least possible flow resistance.
On at least one face of the substrate layer of the system according to the invention there is a functional layer having an average pore diameter less than 1 nm, in particular less than 0.8 nm, particularly preferably less than 0.5 nm, depending on the separation task to be achieved. The functional layer performs the actual separation of the gas molecules. Theoretically, the average pore diameter should be between that of the gas molecules to be 23856 PCT/DE2005/001442 Transl. of WO 2006/032230 separated. However, it has been shown that slightly larger pore diameters also result in a very satisfactory separation rate.
The functional layer consists in particular of Ti02 or Zr02 and may have a particularly thin shape. Advantageous layer thicknesses are in the range of several nm to several hundred nm.
The dimension is dependent on the separation task and the separation efficiencies to be achieved. The selectivity (separation factor a) generally increases with decreasing pore diameter of the functional layer. On the other hand, very small pores, especially in conjunction with a thicker functional layer, reduce the flow rate (permeation) considerably. Thus, the separation is always a balance between selectivity and permeation, and is adapted by one skilled in the art to the particular separation task to be achieved.
For better adhesion it is advantageous to optionally provide an intermediate layer between the substrate layer and the functional layer. This intermediate layer generally comprises oxidic systems, in particular ceramics. Examples of advantageous materials for the intermediate layer are Ti02, Zr02, or A1203. The intermediate layer likewise has a porous structure throughout. The average pore diameter of the intermediate layer is advantageously between that of the substrate layer and that of the functional layer, in particular between 2 and 100 nm. The intermediate layer advantageously has a thickness ranging from 100 nm to 50 m.
In one special embodiment of the invention, a functional layer optionally provided with an intermediate layer is situated on both faces of the substrate layer. The symmetrical arrangement is selected in particular when the individual layers are very thin, since in that case the symmetrical arrangement on both faces 23856= PCT/DE2005/001442 Transl. of WO 2006/032230 advantageously results in additional stability of the separation system. In addition, the symmetrical shape consistently minimizes warping during the sintering process.
In a further advantageous embodiment of the invention, the functional layer, optionally together with an intermediate layer, is present as a graduated layer. The characteristics of the above-referenced intermediate layer are then present in particular at the substrate-layer/graduated-layer interface, whereas the characteristics of the above-referenced functional layer are present in particular at the exposed surface of the laminate. In other words, the average pore diameter of the substrate layer facing the exposed gas/functional-layer surface in principle decreases continuously and in a graduated manner.
Within the scope of the invention, for stability reasons an additional layer having coarser pores may also be provided on the outer functional layer having a very small pore diameter.
To produce the gas separation system according to the invention, first a porous ceramic or metallic film having a layer thickness between 200 and 500 m is prepared as the substrate layer. A cermet may also be used as the substrate layer. The porosities are in the m range. One or more ceramic intermediate layers having pore sizes in the 2-100 nm range are applied on one or both faces, for example. Coating on both faces with the intermediate layer is particularly practical when the aim is to prevent warping of a very thin substrate layer during heat treatment. The functional layer necessary for the actual gas separation may advantageously be applied by use of a sol-gel method. However, chemical vapor deposition (CVD) or physical vapor deposition (PVD) may also be used as application techniques. In 23856 PCT/DE2005/001442 Transl. of WO 2006/032230 the sol-gel method the porosity in the functional layer is set by use of a sol composition under pyrolysis conditions, i.e. burning off the organic components, and sintering conditions.
The gas separation systems (membranes) according to the invention consistently have high permeability, high selectivity, and good stability under conditions of use. They are therefore particularly suited for gas separation of commercially important gases such as N2, 02, C02, H2, He, or CH9 from gas mixtures.
Special description section The subject matter of the invention is described in greater detail below with reference to one illustrated embodiment, without limiting the subject matter of the invention thereto.
A Ti02 intermediate layer (d = 20-30 pm, grain size 200 nm) was applied by wet powder spraying or screen printing to a porous, film-cast steel substrate made of 316 L stainless steel (d = 200-300 m, grain size less than 5 m) presintered at 900 C/1 min. After sintering at 950 C/1 hour under vacuum, a functional layer of Ti02 or alternatively Zr02 was applied. A sol-gel composed of an organic precursor, for example titanium propylate, zirconium propylate, or acetylacetone, and an a-position carboxylic acid was used, and was applied by spin coating or an immersion process.
This was followed by pyrolysis (at 600 C/1 hour, for example) of the organic components of the sol, and final sintering of the sample at temperatures up to 1000 C.
Table of kinetic diameters of gases:
CH4 0.38 nm N2 0.364 nm 02 0.346 nm 23856 PCT/DE2005/001442 Transl. of WO 2006/032230 COZ 0.33 nm H2 0.289 nm He 0.26 nm
The use of disks as substrates results in flat membranes.
The advantage of ceramic membranes compared to polymer filters is that use is made of the high thermal and chemical resistance of the ceramic.
Also known from the Fraunhofer Institute for Ceramic Technologies and Sintered Materials (IKTS) are polymer membranes having layer thicknesses that may be set between 1 and 5 m and that are produced by coating the substrate with a specially prepared organosilicon precursor, followed by polymer pyrolysis.
Various porosities and pore sizes are obtained, depending on the type and molecular structure of the polymer used. One precursor system results in, for example, pore diameters of approximately 1.5 nm with a narrow distribution, and BET surfaces of up to 600 m2/g. Pyrolysis of other polymer classes results in various pore diameters between 4 and 20 nm with a narrow pore size distribution, depending on the molecular structure and the thermolytic conditions. After pyrolysis an opaque, crack-free, highly porous silicon carbide layer is present on the substrate surface that is used as a filter-active separating layer in the membrane filtration process.
For gas phase separation of commercially important gases emitted from a fossil fuel-fired power plant, there are currently over 40 different approaches, of which only the chemical separation 23856 PCT/DE2005/001442 Transl. of WO 2006/032230 technology, i.e. absorption in amine solutions in pilot power plants, has thus far been used on an industrial scale.
For separation by set pore sizes, polymer membranes have been developed for separation in the low-temperature range.
Hydrogen-permeable AgPd membranes and amorphous microporous silica membranes, for example, exist for high-temperature applications up to approximately 500 C. Ionic, mixed, or proton conductors may also be considered.
It is disadvantageous that the chemical processes generally have a high loss in efficiency, whereas the polymer membranes are limited to applications at low temperatures. The maximum operational limits for costly AgPd membranes and for silica membranes is approximately 500 C. It is disadvantageous that these membranes are also sensitive to water.
Object and solution The object of the invention is to provide a system that allows gas separation of commercially important gases such as H2, N2, 02, or CO2 from a gas mixture, in particular at higher temperatures. It is a further object of the invention to provide a method for producing such a system.
The objects of the invention are attained by a system comprising the totality of features according to the main claim, and by a method comprising the totality of features of the independent claims. Advantageous embodiments of the method and the system are given in the subclaims that respectively refer to the main and/or independent claims.
Subject matter of the invention Within the scope of the invention it has been found that a thin membrane comprising a metallic and/or ceramic substrate 23856 PCT/DE2005/001442 Transl. of WO 2006/032230 layer and an oxidic functional layer provided thereon has an effective separation factor for the separation of gases.
The substrate layer has an advantageous effect on the mechanical stability of the membrane, and in particular may be composed of steel, for example 316 L stainless steel and/or a ceramic. The thickness of the substrate layer depends on the separation task, and may vary between 100 pm and 1 mm. The thickness of the substrate layer influences the permeation rate, and in principle should therefore be as thin as possible, in particular less than 1 mm. However, in order to meet their function as a substrate layer it is desirable and advantageous to have layer thicknesses of at least 100 m, preferably 200 pm.
Metallic substrate layers generally have better stability than ceramic layers of a comparable layer thickness.
The substrate layer itself has a porous structure throughout, with an average pore size in the m range. The average pore diameter may be determined in particular by scanning electron microscopy (SEM), or, for smaller pore diameters, by transmission electron microscopy (TEM). The pores are selected to be much larger than those in the adjacent functional layer. The substrate layer should provide mechanical stability while producing the least possible flow resistance.
On at least one face of the substrate layer of the system according to the invention there is a functional layer having an average pore diameter less than 1 nm, in particular less than 0.8 nm, particularly preferably less than 0.5 nm, depending on the separation task to be achieved. The functional layer performs the actual separation of the gas molecules. Theoretically, the average pore diameter should be between that of the gas molecules to be 23856 PCT/DE2005/001442 Transl. of WO 2006/032230 separated. However, it has been shown that slightly larger pore diameters also result in a very satisfactory separation rate.
The functional layer consists in particular of Ti02 or Zr02 and may have a particularly thin shape. Advantageous layer thicknesses are in the range of several nm to several hundred nm.
The dimension is dependent on the separation task and the separation efficiencies to be achieved. The selectivity (separation factor a) generally increases with decreasing pore diameter of the functional layer. On the other hand, very small pores, especially in conjunction with a thicker functional layer, reduce the flow rate (permeation) considerably. Thus, the separation is always a balance between selectivity and permeation, and is adapted by one skilled in the art to the particular separation task to be achieved.
For better adhesion it is advantageous to optionally provide an intermediate layer between the substrate layer and the functional layer. This intermediate layer generally comprises oxidic systems, in particular ceramics. Examples of advantageous materials for the intermediate layer are Ti02, Zr02, or A1203. The intermediate layer likewise has a porous structure throughout. The average pore diameter of the intermediate layer is advantageously between that of the substrate layer and that of the functional layer, in particular between 2 and 100 nm. The intermediate layer advantageously has a thickness ranging from 100 nm to 50 m.
In one special embodiment of the invention, a functional layer optionally provided with an intermediate layer is situated on both faces of the substrate layer. The symmetrical arrangement is selected in particular when the individual layers are very thin, since in that case the symmetrical arrangement on both faces 23856= PCT/DE2005/001442 Transl. of WO 2006/032230 advantageously results in additional stability of the separation system. In addition, the symmetrical shape consistently minimizes warping during the sintering process.
In a further advantageous embodiment of the invention, the functional layer, optionally together with an intermediate layer, is present as a graduated layer. The characteristics of the above-referenced intermediate layer are then present in particular at the substrate-layer/graduated-layer interface, whereas the characteristics of the above-referenced functional layer are present in particular at the exposed surface of the laminate. In other words, the average pore diameter of the substrate layer facing the exposed gas/functional-layer surface in principle decreases continuously and in a graduated manner.
Within the scope of the invention, for stability reasons an additional layer having coarser pores may also be provided on the outer functional layer having a very small pore diameter.
To produce the gas separation system according to the invention, first a porous ceramic or metallic film having a layer thickness between 200 and 500 m is prepared as the substrate layer. A cermet may also be used as the substrate layer. The porosities are in the m range. One or more ceramic intermediate layers having pore sizes in the 2-100 nm range are applied on one or both faces, for example. Coating on both faces with the intermediate layer is particularly practical when the aim is to prevent warping of a very thin substrate layer during heat treatment. The functional layer necessary for the actual gas separation may advantageously be applied by use of a sol-gel method. However, chemical vapor deposition (CVD) or physical vapor deposition (PVD) may also be used as application techniques. In 23856 PCT/DE2005/001442 Transl. of WO 2006/032230 the sol-gel method the porosity in the functional layer is set by use of a sol composition under pyrolysis conditions, i.e. burning off the organic components, and sintering conditions.
The gas separation systems (membranes) according to the invention consistently have high permeability, high selectivity, and good stability under conditions of use. They are therefore particularly suited for gas separation of commercially important gases such as N2, 02, C02, H2, He, or CH9 from gas mixtures.
Special description section The subject matter of the invention is described in greater detail below with reference to one illustrated embodiment, without limiting the subject matter of the invention thereto.
A Ti02 intermediate layer (d = 20-30 pm, grain size 200 nm) was applied by wet powder spraying or screen printing to a porous, film-cast steel substrate made of 316 L stainless steel (d = 200-300 m, grain size less than 5 m) presintered at 900 C/1 min. After sintering at 950 C/1 hour under vacuum, a functional layer of Ti02 or alternatively Zr02 was applied. A sol-gel composed of an organic precursor, for example titanium propylate, zirconium propylate, or acetylacetone, and an a-position carboxylic acid was used, and was applied by spin coating or an immersion process.
This was followed by pyrolysis (at 600 C/1 hour, for example) of the organic components of the sol, and final sintering of the sample at temperatures up to 1000 C.
Table of kinetic diameters of gases:
CH4 0.38 nm N2 0.364 nm 02 0.346 nm 23856 PCT/DE2005/001442 Transl. of WO 2006/032230 COZ 0.33 nm H2 0.289 nm He 0.26 nm
Claims (21)
1. A system for gas separation comprising a laminate, characterized by a mechanically stable metallic substrate layer that is formed through with open pores and that has an average porosity in the µm range, and a functional layer composed of TiO2 and/or ZrO2 that is formed throughout with pores and that has an average pore diameter of less than 1 nm, provided on at least one face of the substrate layer.
2. The system according to preceding claim 1 wherein there is a respective such two functional layer on each of the faces of the substrate layer.
3. The system according to one of the preceding claims 1 and 2 wherein the substrate layer has a thickness between 100 µm and 1 mm, in particular between 200 µm and 500 µm.
4. The system according to one of the preceding claims 1 or 3 wherein an intermediate layer is provided between the substrate layer and at least one functional layer.
5. The system according to preceding claim 4 wherein the intermediate layer is composed of Al2O3, TiO2, and/or ZrO2.
6. The system according to one of the preceding claims 4 and 5 wherein the intermediate layer has a thickness between 100 nm and 100 µm, in particular between 20 µm and 50 µm.
7. The system according to one of the preceding claims 1 through 6 wherein the functional layer has an average pore diameter of less than 0.8 nm, in particular less than 0.5 nm.
8. The system according to one of the preceding claims 1 through 7 wherein the functional layer is structured as a graduated layer.
9. The system according to preceding claim 8 wherein the average pore diameter of the functional layer varies continuously and/or in a graduated manner.
10. The system according to one of the preceding claims 8 and 9 wherein the average pore diameter of the substrate layer decreases away from the exposed surface of the functional layer/gas.
11. A method for producing a system for gas separation comprising a laminate wherein a functional layer composed of TiO2 and/or ZrO2 and having an average pore diameter of less than 1 nm is applied to at least one face of a metallic substrate layer that is porous throughout.
12. The method according to preceding claim 11 wherein a functional layer composed of TiO2 and/or ZrO2 and having an average pore diameter of less than 1 nm is applied to both faces of the substrate layer.
13. The method according to one of preceding claims 11 and 12 wherein a substrate layer having a thickness between 100 µm and 1 mm, in particular between 200 µm and 500 µm, is used.
14. The method according to one of the preceding claims 11 through 13 wherein an intermediate layer is provided between the substrate layer and at least one functional layer.
15. The method according to one of the preceding claims 11 through 14 wherein the intermediate layer is composed of Al2O3, TiO2, and/or ZrO2.
16. The method according to one of the preceding claims 11 through 15 wherein the intermediate layer has a thickness between 100 nm and 100 µm, in particular between 20 µm and 50 µm.
17. The method according to one of the preceding claims 11 through 16 wherein a functional layer having an average pore diameter of less than 0.8 nm, in particular less than 0.5 nm, is applied.
18. The method according to one of the preceding claims 11 through 17 wherein the functional layer is applied as a graduated layer.
19. The method according to preceding claim 18 wherein the average pore diameter of the functional layer varies continuously and/or in a graduated manner.
20. The method according to one of the preceding claims 11 through 19 wherein the average pore diameter of the substrate layer decreases away from the exposed surface of the functional layer/gas.
21. The method according to one of the preceding claims 11 through 20 wherein the functional layer and/or the intermediate layer is applied using a sol-gel process.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE200410046310 DE102004046310A1 (en) | 2004-09-24 | 2004-09-24 | Device for gas separation and method for producing such a device |
DE102004046310.7 | 2004-09-24 | ||
PCT/DE2005/001442 WO2006032230A1 (en) | 2004-09-24 | 2005-08-13 | Device for gas separation and method for producing one such device |
Publications (1)
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CA2581419A1 true CA2581419A1 (en) | 2006-03-30 |
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CA 2581419 Withdrawn CA2581419A1 (en) | 2004-09-24 | 2005-08-13 | System for gas separation and method for producing such a system |
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US (1) | US8016924B2 (en) |
EP (1) | EP1791624A1 (en) |
JP (1) | JP2008514387A (en) |
CN (1) | CN101031352A (en) |
AU (1) | AU2005287770B2 (en) |
CA (1) | CA2581419A1 (en) |
DE (1) | DE102004046310A1 (en) |
WO (1) | WO2006032230A1 (en) |
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IL175270A0 (en) * | 2006-04-26 | 2006-09-05 | Acktar Ltd | Composite inorganic membrane for separation in fluid systems |
US20100251888A1 (en) * | 2007-11-20 | 2010-10-07 | Curtis Robert Fekety | Oxygen-Ion Conducting Membrane Structure |
DE102008016158A1 (en) | 2008-03-28 | 2009-10-01 | Forschungszentrum Jülich GmbH | Oxygen permeable membrane and process for its preparation |
US8834604B2 (en) * | 2010-09-16 | 2014-09-16 | Volt Research, Llc | High temperature gas processing system and method for making the same |
CN103521089B (en) * | 2013-10-18 | 2015-08-05 | 北京中天元环境工程有限责任公司 | Diffusion barrier |
CN103521074B (en) * | 2013-10-18 | 2015-05-20 | 北京中天元环境工程有限责任公司 | Double-faced separating membrane |
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ES8706772A1 (en) | 1985-03-29 | 1987-06-16 | Sumitomo Naugatuck | Thermoplastic resin composition. |
GB8812217D0 (en) * | 1988-05-24 | 1988-06-29 | Alcan Int Ltd | Composite membranes |
US5605628A (en) | 1988-05-24 | 1997-02-25 | North West Water Group Plc | Composite membranes |
JPH0243928A (en) * | 1988-08-01 | 1990-02-14 | Ngk Insulators Ltd | Inorganic porous membrane |
JPH03143535A (en) * | 1989-10-26 | 1991-06-19 | Toto Ltd | Asymmetric ceramic film and production thereof |
DE4117284A1 (en) | 1991-05-27 | 1992-12-03 | Studiengesellschaft Kohle Mbh | METHOD FOR PRODUCING MICROPOROUS CERAMIC MEMBRANES FOR THE SEPARATION OF GAS AND LIQUID MIXTURES |
DE4303610A1 (en) | 1993-02-09 | 1994-08-11 | Studiengesellschaft Kohle Mbh | Process for the production of poison-proof catalysts |
US6464881B2 (en) | 1996-10-21 | 2002-10-15 | Orelis | Inorganic nanofiltration membrane and its application in the sugar industry |
US6156283A (en) * | 1998-03-23 | 2000-12-05 | Engelhard Corporation | Hydrophobic catalytic materials and method of forming the same |
JP2972876B1 (en) * | 1998-06-16 | 1999-11-08 | 工業技術院長 | Alcohol vapor blocking film in the gas phase |
JP2000233119A (en) * | 1999-02-12 | 2000-08-29 | Toyota Motor Corp | Hydrogen purifying membrane |
JP3660850B2 (en) * | 2000-03-24 | 2005-06-15 | 新日本製鐵株式会社 | Multilayer ceramic material and oxygen separator |
JP2003210951A (en) * | 2002-01-23 | 2003-07-29 | Kyocera Corp | Hydrogen separation filter, its manufacturing method and hydrogen concentrator |
US6854602B2 (en) * | 2002-06-04 | 2005-02-15 | Conocophillips Company | Hydrogen-selective silica-based membrane |
JP2004089838A (en) | 2002-08-30 | 2004-03-25 | Kyocera Corp | Separation membrane module and its manufacturing method |
KR100534013B1 (en) * | 2003-09-04 | 2005-12-07 | 한국화학연구원 | Titania composite membrane for water/alcohol separation, and Preparation thereof |
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2004
- 2004-09-24 DE DE200410046310 patent/DE102004046310A1/en not_active Withdrawn
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2005
- 2005-08-13 EP EP05774386A patent/EP1791624A1/en not_active Withdrawn
- 2005-08-13 AU AU2005287770A patent/AU2005287770B2/en not_active Ceased
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- 2005-08-13 US US11/663,551 patent/US8016924B2/en not_active Expired - Fee Related
- 2005-08-13 WO PCT/DE2005/001442 patent/WO2006032230A1/en active Application Filing
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DE102004046310A1 (en) | 2006-04-06 |
WO2006032230A1 (en) | 2006-03-30 |
AU2005287770A1 (en) | 2006-03-30 |
EP1791624A1 (en) | 2007-06-06 |
US8016924B2 (en) | 2011-09-13 |
JP2008514387A (en) | 2008-05-08 |
AU2005287770B2 (en) | 2010-02-04 |
US20090193975A1 (en) | 2009-08-06 |
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